U.S. patent number 9,556,403 [Application Number 13/395,027] was granted by the patent office on 2017-01-31 for method for preparing polyols and products obtained.
This patent grant is currently assigned to CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE. The grantee listed for this patent is Carine Alfos, Rachida Bakhiyi, Aurelie Boyer, Eric Cloutet, Henri Cramail. Invention is credited to Carine Alfos, Rachida Bakhiyi, Aurelie Boyer, Eric Cloutet, Henri Cramail.
United States Patent |
9,556,403 |
Cramail , et al. |
January 31, 2017 |
Method for preparing polyols and products obtained
Abstract
The present invention relates to a method for preparing polyols
of formula (I'') ##STR00001## R'.sub.1 being H or an alkyl group,
R'' being especially an alkyl group, A.sub.1, being an alkylene
radical and R.sub.3, are being especially a group -A.sub.2-O--Y',
A.sub.2 being an alkylene radical and Y' being especially H, said
method especially comprising a step of epoxidation of a compound of
formula ##STR00002## R''.sub.1 being H or an alkyl group, A.sub.t
being defined as above in formula (I'') and R.sub.4 being
especially a group -A.sub.2-O--Y.sub.1', A.sub.2 being defined as
above in formula (I'') and Y'.sub.1 being especially H, in order to
obtain a compound of formula ##STR00003## A.sub.1 being defined as
above, R'''.sub.1 being H or an alkyl group and R.sub.5 being
especially a group of formula -A.sub.2-O--Y.sub.2', A.sub.2 being
as defined above in formula (I'') and Y'.sub.2 being especially
H.
Inventors: |
Cramail; Henri (Pessac,
FR), Boyer; Aurelie (Bourdeaux, FR),
Cloutet; Eric (Sant Caprais de Bordeaux, FR),
Bakhiyi; Rachida (Merignac, FR), Alfos; Carine
(Pessac, FR) |
Applicant: |
Name |
City |
State |
Country |
Type |
Cramail; Henri
Boyer; Aurelie
Cloutet; Eric
Bakhiyi; Rachida
Alfos; Carine |
Pessac
Bourdeaux
Sant Caprais de Bordeaux
Merignac
Pessac |
N/A
N/A
N/A
N/A
N/A |
FR
FR
FR
FR
FR |
|
|
Assignee: |
CENTRE NATIONAL DE LA RECHERCHE
SCIENTIFIQUE (Paris, FR)
|
Family
ID: |
41530793 |
Appl.
No.: |
13/395,027 |
Filed: |
September 10, 2010 |
PCT
Filed: |
September 10, 2010 |
PCT No.: |
PCT/FR2010/051894 |
371(c)(1),(2),(4) Date: |
September 19, 2012 |
PCT
Pub. No.: |
WO2011/030076 |
PCT
Pub. Date: |
March 17, 2011 |
Prior Publication Data
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|
|
Document
Identifier |
Publication Date |
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US 20130005937 A1 |
Jan 3, 2013 |
|
Foreign Application Priority Data
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|
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Sep 11, 2009 [FR] |
|
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09 56260 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11C
3/003 (20130101); C07C 67/31 (20130101); C07D
303/40 (20130101); C08G 18/36 (20130101); C07C
69/732 (20130101); C07C 67/03 (20130101); C07D
303/44 (20130101); C07D 303/42 (20130101); C07C
67/03 (20130101); C07C 69/58 (20130101); C07C
67/31 (20130101); C07C 69/732 (20130101) |
Current International
Class: |
C07C
67/31 (20060101); C07D 303/40 (20060101); C07C
69/732 (20060101); C07C 67/03 (20060101); C11C
3/00 (20060101); C07C 69/675 (20060101); C08G
18/36 (20060101); C07D 405/12 (20060101); C07D
303/42 (20060101); C07D 303/44 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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H04-163451 |
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Jun 1992 |
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JP |
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H04-364195 |
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Dec 1992 |
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JP |
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H09-222707 |
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Aug 1997 |
|
JP |
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H10-319551 |
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Dec 1998 |
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JP |
|
2007-56157 |
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Mar 2007 |
|
JP |
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WO 03/093215 |
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Nov 2003 |
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WO |
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WO 2005-090501 |
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Sep 2005 |
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WO |
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WO 2009/058367 |
|
May 2009 |
|
WO |
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WO 2011/029738 |
|
Apr 2011 |
|
WO |
|
Other References
Derwent Abstract of JP 2010-069377A Apr. 2, 2010. cited by examiner
.
International Search Report for corresponding International
Application No. PCT/FR2010/051894, dated Jan. 24, 2011. cited by
applicant.
|
Primary Examiner: Washville; Jeffrey
Attorney, Agent or Firm: Davidson, Davidson and Kappel,
LLC
Claims
What is claimed is:
1. A method for preparing a polyol fitting the general formula (I):
##STR00083## wherein: R.sub.1 represents H or a linear or branched
alkyl group, comprising from 2 to 14 carbon atoms, R' represents a
linear or branched alkyl group, comprising from 1 to 18 carbon
atoms, A.sub.1 represents a linear or branched divalent alkylene
radical, comprising from 2 to 14 carbon atoms, A.sub.2 represents a
linear divalent alkylene radical, comprising from 1 to 10 carbon
atoms, if necessary comprising one or more substituents, Y
represents a hydrogen atom or a group of formula (A) ##STR00084##
A.sub.1, R' and R.sub.1 are as defined above, said method
comprising the following steps: a) a step for transesterification
of a compound of the following formula (II): ##STR00085## R.sub.2
represents a branched or linear alkyl group comprising from 1 to 10
carbon atoms, and R.sub.1- and A.sub.1 being as defined above, with
a diol of the following formula (III): HO-A.sub.2-OH (III) in order
to obtain a compound of the following formula (IV): ##STR00086##
A.sub.1, A.sub.2 and R.sub.1 being as defined above in formula (I),
Y.sub.1 representing a hydrogen atom or a group of formula
(A.sub.1) ##STR00087## A.sub.1 and R.sub.1 being as defined above,
b) a step for epoxidation of the compound of the aforementioned
formula (IV) in order to obtain a compound of the following formula
(V): ##STR00088## A.sub.1, A.sub.2 and R.sub.1 being as defined
above, Y.sub.2 representing a hydrogen atom or a group of formula
(A.sub.2) ##STR00089## A.sub.1 and R.sub.1 being as defined above,
c) a step for opening the epoxide ring with an alcohol of formula
R'OH, R' being as defined above, in order to obtain a compound of
formula (I) as defined above, and d) a step for recovering the
compound of formula (I) as defined above.
2. The method for preparing a diol according to claim 1,
characterized in that the diol fits the following formula (I-1):
##STR00090## A.sub.1, A.sub.2, R.sub.1 and R' being as defined in
claim 1, or the following formula (I-2): ##STR00091## A.sub.1,
A.sub.2, R.sub.1 and R' being as defined in claim 1.
3. The method for preparing a polyol according to any of claim 1,
wherein step a) is carried out in the presence of a catalyst
selected from the group consisting of magnesium oxide, zinc acetate
and sodium methanolate.
4. The method for preparing a polyol according to claim 3, wherein
step a) is carried out a temperature comprised between from 150 to
200.degree. C. under nitrogen flow.
5. The method according to claim 3, wherein step a) is carried out
without solvent.
6. The method for preparing a polyol according to claim 1, wherein
step b) is carried out in the presence of a peracid.
7. The method for preparing a polyol according to claim 6, wherein
step b) is carried out in the presence of a peracid selected from
the group consisting of metachloroperbenzoic acid (m-CPBA) and of
magnesium monoperoxyphthalate hexahydrate peracid (MMPP).
8. The method for preparing a polyol according to claim 1, wherein
step c) is carried out in the presence of a catalyst selected from
the group consisting of an acid catalyst of the proton ion exchange
resin, of heterogeneous catalysts, of para-toluenesulfonic acid
(PTSA) and of methanesulfonic acid (MSA), at a temperature
comprised between from 20.degree. C. to 120.degree. C.
9. The method for preparing a polyol according to claim 8, wherein
the temperature is 70.degree. C.
10. A compound fitting the following general formula (I):
##STR00092## wherein: R.sub.1 represents a linear or branched alkyl
group comprising from 2 to 14 carbon atoms, R' represents a linear
or branched alkyl group, comprising from 1 to 18 carbon atoms,
A.sub.1 represents a linear or branched divalent alkylene radical,
comprising from 2 to 14 carbon atoms, A.sub.2 represents a linear
divalent alkylene radical, comprising from 1 to 10 carbon atoms, if
necessary comprising one or more substituents, and Y represents a
hydrogen atom or a group of formula (A) ##STR00093## A.sub.1, R'
and R.sub.1 being as defined above.
11. Intermediate compounds chosen from the group consisting of:
--compound (3) having the following formula: ##STR00094## wherein
Y.sub.2 represents A.sub.2, A.sub.2 being as defined in claim 1;
and compounds having the following formula: ##STR00095## A.sub.1
representing a C.sub.7H.sub.14 radical, R.sub.1 representing an
alkyl group comprising 9 carbon atoms, and A.sub.2 represents a
radical selected from the following radicals: C.sub.3H.sub.6,
C.sub.4H.sub.8, C.sub.5H.sub.10, C.sub.6H.sub.12,
H.sub.2C--(CH.sub.2OCH.sub.2).sub.6--CH.sub.2,
H.sub.2C--(CH.sub.2OCH.sub.2).sub.13--CH.sub.2,
H.sub.2C--(CH.sub.2OCH.sub.2).sub.45--CH.sub.2 or
H.sub.2C--C.sub.6H.sub.4--CH.sub.2.
12. Polymers as obtained by polymerization of a compound as defined
in claim 10 and of a (poly)isocyanate.
Description
This application is a national phase application under 35 U.S.C.
.sctn.371 of International Application No. PCT/FR2010/051894 filed
on Sep. 10, 2010, which claims priority to French Application No.
0956260, filed on Sep. 11, 2009, the disclosures of which are all
hereby incorporated by reference herein.
The present invention relates to a novel method for preparing
polyols, notably diols as well as the novel polyols obtained.
BACKGROUND
There exist different approaches for synthesizing polymers from
vegetable oils. The first, the most widespread consists of
considering triglycerides as base materials, the latter being able
to be epoxidized and then for example alcoholized or hydro
formulated, in order to make them functionable and
polymerizable.
An oil is a mixture of triglycerides (triesters) formed by
condensation of fatty acids and of glycerol. The high number of
types of fatty acids (up to 24) present in each fat and the
multiple possibilities of their combinations with glycerol
molecules ensure that fats are highly complex mixtures of
compounds, the properties of which vary from one oil to another.
The nature of the triglycerides may therefore vary within a same
oil.
The reactive sites present in a triglyceride are mainly double
bonds and ester functions. The reactivity of double bonds allows
the introduction of hydroxyl functions, thereby allowing access to
multihydroxlated monomers. It is nevertheless impossible to obtain
triglycerides having perfectly defined structures and
functionalities.
The synthesis of polyols from vegetable oil is well described in
the literature since the latter are excellent precursors for
synthesizing polymers. These materials have one popularity because
of the natural origin of the precursors and of the attractive
properties provided by the structure and the composition of the
vegetable oils. The reactive sites in all fats are ester functions
and double bonds. Certain oils also have other groups such as
hydroxyls or epoxides.
The double bonds of these compounds are generally not sufficiently
reactive for being used as sites of radical polymerization.
Nevertheless, at a high temperature (330.degree. C.), the double
bonds may migrate along the backbone in order to form conjugate
sites, which facilitates condensations of the Diels-Alder type.
Oligomers were synthesized by vulcanization of oils with sulfur
monochloride and used as additives in the gum industry for example.
Oligomers were also synthesized by cationic polymerization in the
presence of boron trifluoride (Croston et al., J. Amer. Oil Chem.
Soc. 1952, 331-333), for application in the formulations of inks.
Other reactions involving double bonds, such as polymerization by
metathesis gave the possibility of obtaining oligomers (Refvik et
al., J. Amer. Oil Chem. Soc. 1999, 76, 93-98) and the materials
which stem from this are rarely utilizable because they are very
poorly defined.
It is therefore necessary to better control functionalization of
the vegetable oils.
As already indicated, the presence of double bonds on the backbone
allows introduction of hydroxyl groups. The latter may be achieved
by direct oxidation of the double bonds, which consists of having
an oxygen screen pass through the oil heated to 135.degree. C. (G.,
Soucek et al. "Spectroscopic investigation of blowing process of
soybean oil", Surface Coatings International, Part B, Coatings
Transactions. 2003, 86: 221-229). Control of the oxidation is not
satisfactory and many byproducts are formed such as peroxides,
aldehydes, ketones, splittings of chains, etc. The only advantage
of these polyols is their low price cost and their synthesis is
achieved in a single step, in spite of the many treatments applied
to the final product (odors, high acid index, dark color,
etc.).
An organometal catalyst may also be used in order to better control
the oxidation reaction (WO2006/094227; WO2007/143135) in the
presence of an oxidant.
Polyols having primary hydroxyls may be prepared by hydro
formulation of the unsaturations (Guo et al., J. of Polymers and
the Environment. 2002, 10: 49-52). This method involves a reaction
between carbon monoxide and dihydrogen, causing the formation of an
aldehyde group which is converted into a hydroxyl by hydrogenation.
Rhodium-based catalysts generally used are very efficient
(conversions close to 100%) but also very costly. Conversely,
cobalt-based catalysts are inexpensive but less efficient. By
ozonolysis of the double bonds, it is also possible to obtain
polyols having terminal hydroxyl groups (Guo et al., J. of Polymer
Sci., 2000, 38: 3900-3910). The ozone passes through a solution of
vegetable oil and ethylene glycol, in the presence of an alkaline
catalyst.
Another route for accessing polyols consists of conducting a
preliminary reaction of epoxidation of the unsaturations. Many
studies described in the literature describe the epoxidation of
fats (Swern, et al. J. Am. Chem. Soc. 1944, 66, 1925-1927; Findley
et al., J. Am. Chem. Soc. 1945, 67, 412-414: U.S. Pat. No.
5,026,881; U.S. Pat. No. 3,328,430; Petrovi et al., Eur. J. Lipid
Sci. Technol. 2002, 104: 293-299 and U.S. Pat. No. 4,647,678).
Petrovic recently demonstrated the possibility of achieving
epoxidation of vegetable oil via an enzymatic route (Vic{hacek over
( )}ek, T. et al., J. Amer. Oil Chem. Soc. 2006, 83: 247-252) or
catalyzed with an ion exchange resin (Sinadinovi -Fis{hacek over (
)}er et al., J. Amer. Oil Chem. Soc. 2001, 78: 725). Nevertheless
the most common route is the use of a peracid formed in situ,
generally hydrogen peroxide in the presence of a carboxylic acid
(most often formic acid in a catalytic amount). The reaction is
conducted between 50 and 80.degree. C. for 1 to 4 hours.
It is important to emphasize that the epoxidation of fats already
having a primary alcohol at the end of the chain was never achieved
from a peracid formed in situ. This reaction cannot be conducted
under the same conditions as previously because of secondary
reactions between the carboxylic acid and the terminal alcohol.
The epoxidized vegetable oils were used as intermediates in many
syntheses. The Petrovic group describes the opening of the epoxides
with alcohols, inorganic acids and by hydrogenation under acid
catalyses (Guo et al., J. Polym. Sci. Part A: Polym. Chem. 2000,
38: 3900-3910). Epoxidized triglycerides were modified by reaction
with HCl or HBr in the presence of acetone (solvent) by
hydrogenation with H.sub.2 in the presence of isopropanol and of
Raney nickel as a catalyst, and finally by methanol in the presence
of isopropanol and of an acid catalyst (for example fluoboric
acid).
These functional triglycerides have different reactivities: the one
derived from the opening with methanol being the most reactive
towards isocyanates for the chemistry of polyurethanes. Petrovic
increases the reactivity of the polyols obtained by ethoxylation
(opening of ethylene oxide by the secondary alcohol under acid
catalyses), which converts the secondary alcohols into primary
alcohols. However it is noted that the use of an acid catalyst
causes secondary reactions, such as the formation of a methyl ester
during the opening of the epoxide with methanol. The solution lies
in the use of a specific catalyst for opening the epoxide and
operating at lower temperatures in order to avoid secondary
coupling reactions. Finally, it is interesting to note that the US
Patent Application, published under number 2006/7045577, describes
the synthesis of polyurethane from soya bean oil according to a
two-step process: (i) the oil is epoxidized from conventional
methods using a peracid and (ii) the epoxidized soya bean oil
reacts with carbon dioxide in order to give a carbonated vegetable
oil. The reaction of this product with a diamine allows access to a
polyurethane without using any isocyanates.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a method for
preparing polyols from vegetable oil esters giving the possibility
of getting rid of the aforementioned drawbacks.
The object of the present invention is also to provide a method for
preparing polyols comprising the use of catalysts better meeting
environmental expectations than most homogeneous catalysts used and
which limit the secondary reactions.
The object of the present invention is also to provide a method
which, unlike the method of the prior art which relate to the
chemical transformation from triglycerides having poorly defined
structures, consists in a simple and efficient route for chemical
modification of monoesters or of triglycerides in order to obtain
functional precursors with controlled functionality.
The object of the present invention is to provide a simple
preparation method in three steps via mono- or di-esters of
vegetable oil.
An object of the present invention is to provide a three step
method allowing access to novel synthons, mono-esters of di-esters,
all at least bifunctional (polyols) and having well defined
structures and requiring a specific catalyse.
The present invention relates to a method for preparing a polyol
fitting the following general formula (I''):
##STR00004##
wherein: R'.sub.1 represents H or a linear or branched alkyl group
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally be substituted with one or more OR.sub.a groups, R.sub.a
representing H or a group R' as defined below, A.sub.1 represents a
linear or branched divalent alkylene radical, comprising from 2 to
14 carbon atoms, R'' represents: a linear or branched alkyl group
R', comprising from 1 to 18 carbon atoms, or a group of formula
-A.sub.2-OH, A.sub.2 representing a linear or branched divalent
alkylene radical, comprising from 1 to 10 carbon atoms, if
necessary comprising one or more substituents, notably selected
from the group formed by the phenylene radical and the radical of
formula --(CH.sub.2OCH.sub.2).sub.n--, n representing an integer
comprised between 1 to 100, preferably from 6 to 50, and preferably
equal to 6, 13 or 45, A.sub.2 preferably representing a radical of
formula --CH.sub.2-A.sub.3-CH.sub.2--, A.sub.3 representing a group
of formula --(CH.sub.2OCH.sub.2).sub.n--, n representing an integer
comprised between from 1 to 100, and preferably equal to 6, 13 or
45, or a phenylene radical, R.sub.3 represents: a linear or
branched alkyl group R.sub.2, comprising from 1 to 10, preferably
from 1 to 6 carbon atoms, or a group of formula -A.sub.2-O--Y',
A.sub.2 being as defined as above and Y' representing a hydrogen
atom or a group of formula (A')
##STR00005##
A.sub.1, R' and R'.sub.1 being as defined above in formula
(I''),
it being understood that when R'' is a group R' then R.sub.3
represents a group of formula -A.sub.2-O--Y', and when R'' is a
group -A.sub.2-OH then R.sub.3 represents a group R.sub.2,
said method comprising the following steps:
a) a step for epoxidation of the compound of the following formula
(IV''):
##STR00006##
A.sub.1 being as defined above in formula (I''),
R''.sub.1 representing H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally contain one or 2 double bonds, and said alkyl group may
also if necessary be substituted with an OH group,
R.sub.4 representing an alkyl group R.sub.2 as defined above, or a
group of formula -A.sub.2-O--Y.sub.1', A.sub.2 being as defined
above and Y'.sub.1 representing a hydrogen atom or a group of
formula (A'.sub.1)
##STR00007##
A.sub.1 being as defined above in formula (I'') and R''.sub.1 being
as defined above in formula (IV''),
in order to obtain a compound of the following formula (V''):
##STR00008##
A.sub.1 being as defined above in formula (I''),
R'''.sub.1 representing H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally contain one or two epoxide groups, and said alkyl group
may also if necessary be substituted with an OH group,
R.sub.5 representing an alkyl group R.sub.2 as defined above, or a
group of formula -A.sub.2-O--Y.sub.2', A.sub.2 being as defined
above and Y'.sub.2 representing a hydrogen atom or a group of
formula (A'.sub.2)
##STR00009##
A.sub.1 being as defined above in formula (I'') and R'''.sub.1
being as defined above in formula (V''), and
b) a step for opening the epoxide ring of the compound of formula
(V'') with an alcohol of formula R''OH, R'' being as defined above,
in order to obtain a compound of formula ('') as defined above,
and
c) a step for recovering the compound of formula (I'') as defined
above.
The initial compound of formula (IV'') encompasses both the
compounds (IV') and (IV''-1):
##STR00010##
The compound (IV''-1) is obtained by transesterification of a
vegetable oil, notably sunflower, rape seed or castor oil, with an
alcohol R.sub.2OH, and the compound (IV') is obtained by
transesterification of the compound (IV''-1) with a diol
HO-A.sub.2-OH.
When the epoxidation step a) is carried out on a compound (IV''-1),
a compound (V''-1) is then obtained:
##STR00011##
When the epoxidation step a) is carried out on a compound (IV'), a
compound (V'') is then obtained:
##STR00012##
When the step for opening the ring b) is carried out on a compound
(V''-1), a compound (I''-1) is then obtained:
##STR00013##
The compound for formula (I''-1) is a compound of the monoester
type comprising at least two hydroxyl functions. It may optionally
contain other hydroxyl functions depending on the nature of
R'.sub.1.
When the step for opening the ring b) is carried out on a compound
(V'), a compound (I') is then obtained:
##STR00014##
The compound of formula (I') is a compound of the monoester or
diester type (depending on the nature of Y') comprising at least
two hydroxyl functions. It may optionally contain other hydroxyl
functions depending on the nature of R'.sub.1.
The initial product (IV'') contains a group R''.sub.1 which may
optionally contain one or two double bonds. Thus, during the
epoxidation step leading to the compound (V''), these double bonds
may also be epoxidized whence the nature of the group R'''.sub.1.
Finally, during the step for opening the ring, the epoxide groups
present in the group R'''.sub.1 are then also modified, whence the
aforementioned definition of R'.sub.1 and therefore the optional
presence of one or two hydroxyl groups in R'.sub.1.
According to an embodiment, the method of the invention relates to
a method for preparing a polyol fitting the following general
formula (I''-1):
##STR00015##
wherein: R'.sub.1 represents H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally be substituted with one or several OR.sub.a groups,
R.sub.a representing H or a group R' as defined below, A.sub.1
represents a linear or branched divalent alkylene radical
comprising from 2 to 14 carbon atoms, A.sub.2 represents a linear
or branched divalent alkylene radical, comprising from 1 to 10
carbon atoms, if necessary comprising one or more substituents,
notably selected from the group consisting of the phenylene radical
and the radical of formula --(CH.sub.2OCH.sub.2).sub.n--, n
representing an integer comprised between from 1 to 100, preferably
from 6 to 50, and preferentially equal to 6, 13 or 45, A.sub.2
preferably representing a radical of formula
--CH.sub.2-A.sub.3-CH.sub.2--, A.sub.3 representing a group of
formula --(CH.sub.2OCH.sub.2).sub.n--, n representing an integer
comprised between from 1 to 100 and preferably equal to 6, 13 or
45, or a phenylene radical, R.sub.2 represents a linear or branched
alkyl group comprising from 1 to 10, preferably from 1 to 6 carbon
atoms,
said method comprising the following steps:
a) a step for epoxidation of a compound of the following formula
(II'-1):
##STR00016##
R''.sub.1 representing H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally contain one or two double bonds, and said alkyl group
may also if necessary be substituted with an OH group,
A.sub.1 and R.sub.2 being as defined above in formula (I''-1),
in order to obtain a compound of the following formula
(IV''-1):
##STR00017##
A.sub.1 and R.sub.2 being as defined above in formula (I''-1),
R'''.sub.1 representing H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally contain one or two epoxide groups, and said alkyl group
may also if necessary be substituted with an OH group,
b) a step for opening the epoxide ring with a diol of formula
HO-A.sub.2-OH, A.sub.2 being as defined above, in order to obtain a
compound of formula (I''-1) as defined above, and
c) a step for recovering the compound of formula (I''-1) as defined
above.
According to another embodiment, the present invention relates to a
method for preparing a polyol fitting the following general formula
(I'):
##STR00018##
wherein:
R'.sub.1 representing H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally be substituted with one or more OR.sub.a groups, R.sub.a
representing H or a group R' as defined below,
R' represents a linear or branched alkyl group, comprising from 1
to 18 carbon atoms,
A.sub.1 represents a linear or branched divalent alkylene radical,
comprising from 2 to 14 carbon atoms,
A.sub.2 represents a linear or branched divalent alkylene radical,
comprising from 1 to 10 carbon atoms, if necessary comprising one
or more substituents, notably selected from the group consisting of
the phenylene radical and of the radical of formula
--(CH.sub.2OCH.sub.2).sub.n--, n representing an integer comprised
between from 1 to 100, preferably from 6 to 50, and preferentially
equal to 6, 13 or 45,
A.sub.2 preferably representing a radical of formula
--CH.sub.2-A.sub.3-CH.sub.2--, A.sub.3 representing a group of
formula --(CH.sub.2OCH.sub.2).sub.n--, n representing an integer
comprised from 1 to 100, and preferably equal to 6, 13 or 45, or a
phenylene radical,
Y' representing a hydrogen atom or a group of formula (A')
##STR00019##
A.sub.1, R' and R'.sub.1 being as defined above in formula
(I'),
said method comprising the following steps:
a) a step for transesterification of a compound of the following
formula (II'):
##STR00020##
R''.sub.1 representing H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally contain one or two double bonds, and said alkyl group
may also if necessary be substituted with an OH group,
A.sub.1 being as defined above in formula (I'),
R.sub.2 representing a linear or branched alkyl group, comprising
from 1 to 10, preferably from 1 to 6 carbon atoms,
with a diol of the following formula (III): HO-A.sub.2-OH (III)
in order to obtain a compound of the following formula (IV'):
##STR00021##
A.sub.1, A.sub.2 and R''.sub.1 being as defined above,
Y'.sub.1 representing a hydrogen atom or a group of formula
(A'.sub.1)
##STR00022##
A.sub.1 being as defined above in formula (I') and R''.sub.1 being
as defined above in formula (II'),
b) a step for epoxidation of the compound of the aforementioned
formula (IV') in order to obtain a compound of the following
formula (V''):
##STR00023##
A.sub.1 and A.sub.2 being as defined above in formula (I'),
R'''.sub.1 representing H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally contain one or two epoxide groups, and said alkyl group
may also if necessary be substituted with an OH group,
Y'.sub.2 representing a hydrogen atom or a group of formula
(A'.sub.2)
##STR00024##
A.sub.1 being as defined above in formula (I') and R'''.sub.1 being
as defined above in formula (V'),
c) a step for opening the epoxide ring with an alcohol of formula
R'OH, R' being as defined above, in order to obtain a compound of
formula (I') as defined above, and
d) a step for recovering the compound of formula (I') as defined
above.
Thus, the method of the invention consists of synthesizing novel
polymers from fatty acid mono-esters. The latter are generally
obtained for example by transesterification of triglycerides with a
short alcohol (R.sub.2OH, R.sub.2 being as defined above)
preferably with methanol or ethanol.
These esters, and more particularly sunflower or castor methyl or
ethyl esters, were therefore used as base `synthons` in the present
invention.
By using a variety of sunflower oil for which the oleic acid
content is particularly high and by separating by fractionated
distillations the different sunflower oil methyl esters, oleic acid
methyl esters (a single double bond per fatty chain) of high purity
are obtained. It is from this monofunctional precursor that it is
then possible to provide a selected number of hydroxyl groups and
thereby control the functionality of this monomeric `synthon`. A
well defined structure of such monomers is actually indispensable
for elaborating polymeric materials having controlled and
reproducible properties. As the desired polymers are linear, it was
for example sought to create at least difunctional (di-OH) monomers
from oleic sunflower methyl esters.
Within the scope of the present invention, the inventors focused on
the use of catalysts better meeting the environmental expectations
than most homogeneous catalysts used and which limit secondary
reactions. In this sense, heterogeneous catalyses, notably the use
of ion exchange resins is particularly of interest. Such resins are
efficient catalysts for promoting many reactions such as
esterifications, etherifications, transalkylations and alkylations
(G. D. Yadav, P. H. Mehta, Indust. Eng. Chem. Res. 1994, 33:
2198-2208). Heterogeneous catalyses also provides non-negligible
advantages as compared with homogeneous catalyses (recycling,
selectivity and non-toxicity). This novel method was then applied
to the opening of epoxidized fats.
The method of the invention therefore contemplates several routes
for obtaining polyols: a route in three steps via monoesters in
particular comprising the transesterification of vegetable oil
methyl esters for forming mono esters, epoxidation and then opening
of the rings; and a three step route via diesters in particular
comprising the transesterification of vegetable oil methyl esters
in order to form diesters, epoxidation and opening of rings.
The different reactions set into play for the first two methods are
(i) the transesterification of the ester group with diols allowing
the grafting of a first primary hydroxyl function (aforementioned
step a)) (ii) epoxidation of the double bond (aforementioned step
b)), followed by (iii) the opening of the epoxide providing the
second hydroxyl function (aforementioned step c)).
Thus, the present invention allows preparation of polyols fitting
one of the two following formulae:
##STR00025##
i.e., non-symmetrical diols with a primary OH function (at the end
of the chain) and a secondary OH function on the one hand, and
symmetrical diols with two secondary OH functions on the other
hand.
More particularly, the aforementioned method relates to the
preparation of diols. Thus, the present invention also relates to a
method as defined above, for preparing a diol fitting the following
general formula (I):
##STR00026##
wherein:
R.sub.1 representing H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms,
R', A.sub.1 and A.sub.2 are as defined above in formula (I'),
Y represents a hydrogen atom or a group of formula (A)
##STR00027##
A.sub.1, R' and R.sub.1 are as defined above in formula (I'),
said method comprising the following steps:
a) a step for transesterification of a compound of the following
formula (II):
##STR00028##
R.sub.1 is as defined above and R.sub.2 and A.sub.1 are as defined
above in formula (I') and (II'),
with a diol of the following formula (III): HO-A.sub.2-OH (III)
in order to obtain a compound of the following formula (IV):
##STR00029##
A.sub.1, A.sub.2 and R.sub.1 being as defined above in formula
(I),
Y.sub.1 representing a hydrogen atom or a group of formula
(A.sub.1)
##STR00030##
A.sub.1 being as defined above in formula (I) and R.sub.1 being as
defined above in formula (II),
b) a step for epoxidation of the compound of the aforementioned
formula (IV) in order to obtain a compound of the following formula
(V):
##STR00031##
A.sub.1, A.sub.2 and R.sub.1 being as defined above in formula
(I),
Y.sub.2 representing a hydrogen atom or a group of formula
(A.sub.2)
##STR00032##
A.sub.1 being as defined above in formula (I) and R.sub.1 being as
defined above in formula (II),
c) a step for opening the epoxide cycle with an alcohol of formula
R'OH, R' being as defined above, in order to obtain a compound of
formula (I) as defined above, and
d) a step for recovering the compound of formula (I) as defined
above.
The present invention also relates to a method as defined above,
for preparing a diol fitting the general formula (I''-2):
##STR00033##
wherein:
R.sub.1 represents H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms,
R.sub.2, A.sub.1 and A.sub.2 are as defined above in formula
(I''-1), said method comprising the following steps:
a) a step for epoxidation of the compound of formula (II'-2):
##STR00034##
A.sub.1, R.sub.1 and R.sub.2 being as defined above in formula
(I''-2),
in order to obtain a compound of the following formula
(IV''-2):
##STR00035##
A.sub.1, R.sub.1 and R.sub.2 are as defined above,
b) a step for opening the epoxide ring of the compound of formula
(IV''-2) as defined above with a diol of formula HO-A.sub.2-OH,
A.sub.2 being as defined above, in order to obtain a compound of
formula (I''-2) as defined above, and
c) a step for recovering the compound of formula (I''-2) as defined
above.
As indicated earlier, the diols of the invention of formula (I) and
(I''-2) have the particularity of being derived from natural fats
and of having an exact functionality of two.
The method of the invention for preparing the compounds (I) and I')
comprises a first transesterification step carried out in
heterogeneous catalyses (magnesium oxide or another heterogeneous
catalyst) and preferably in the absence of any solvent (clean
synthesis).
The second step of the method of the invention for preparing the
compounds (I) and (I') is an epoxidation and this synthesis is
peculiar because of the presence of the terminal hydroxyl group of
the monoesters. Epoxidation requires the use of a peracid already
formed in order to avoid a secondary reaction with the alcohol at
the end of the chain and the opening of the epoxide is only
possible under relatively mild conditions for inhibiting the
formation of couplings. The specificity of this second step
consists in the use of preformed peracid.
Finally, the third step of the method of the invention for
preparing the compounds (I) and (I') consists of opening the
epoxide with alcohols (methanol, ethanol, propanol, etc.) under
acid catalyses. The specificity of this step consists in that it
preferably applies a recyclable and selective ion exchange resin
and is preferentially carried out in the absence of any solvent. It
is also important to note that these three reactions follow each
other without any intermediate purification (a single purification
may be carried out at the end, which facilitates the setting up of
the method).
Preferably, the method of the invention allows preparation of a
diol fitting the following formula (I-1):
##STR00036## A.sub.1, A.sub.2, R.sub.1 and R' being as defined
above in formula (I).
The diol of formula (I-1) corresponds to a compound of formula (I)
in which Y is a hydrogen atom. This diol comprises a primary OH
function (at the end of the chain) and a secondary OH function.
The present invention also relates to a method for preparing a diol
as defined above, said diol fitting the following formula
(I-2):
##STR00037## A.sub.1, A.sub.2, R.sub.1 and R' are as defined above
in formula (I).
The diol of formula (I-2) corresponds to a compound of formula (I)
in which Y is a group of formula (A). This diol comprises two
secondary OH functions.
According to a preferred embodiment, the step a) of the method of
the invention is carried out in the presence of a catalyst selected
from the group consisting of magnesium oxide, zinc acetate and
sodium methanolate.
Preferably, said step a) is carried out at a temperature comprised
between from 150 to 200.degree. C. under nitrogen flow. This
temperature range is selected depending on the nature of the
catalyst used. For example, if the temperature is above 200.degree.
C., the catalyst is degraded.
According to a preferred embodiment, this step a) as defined above
is carried out without any solvent, which is very advantageous in
terms of ecology.
The present invention also relates to a method for preparing a diol
as defined above, characterized in that the product of formula (IV)
obtained at the end of step a) is in the form of a mixture of
monoesters and diesters, the monoesters fitting the following
formula (IV-1):
##STR00038## and the diesters fitting the following formula
(IV-2):
##STR00039## A.sub.1, A.sub.2 and R.sub.1 being as defined above in
formula (I).
The monoester of formula (IV-1) corresponds to a compound of
formula (IV) wherein Y.sub.1 is H and the diester of formula (IV-2)
corresponds to a formula (IV) in which Y.sub.1 is a group of
formula (A.sub.1).
Within the scope of the method of the present invention, if the
diol, i.e. the compound of formula (III) is used in a large excess
(for example at a molar ratio of 100) (ratio between the number of
moles of the diol (III) and the number of moles of the compound of
formula (II)) up to 95% by weight of monoester (compound of formula
(IV-1)), is obtained, while when the diol is used in default
relatively to the compound of formula (II) (for example with a
molar ratio of 0.5), up to 85% by weight of diester (compound of
formula (IV-2)) is obtained. With the method of the invention it is
therefore possible to control the composition of the obtained
compound (monoester, diester or mixture) by suitably selecting the
amounts of the initial products.
The present invention also relates to a method for preparing a diol
as defined above, characterized in that the product of formula (V)
obtained at the end of step b) is in the form of a mixture of
monoesters and of diesters, the monoesters fitting the following
formula (V-1):
##STR00040## and the diesters fitting the following formula
(V-2):
##STR00041## A.sub.1, A.sub.2 and R.sub.1 are as defined above in
formula (I).
The monoester of formula (V-1) corresponds to a compound of formula
(V) in which Y.sub.2 is H and the diester of formula (V-2)
corresponds to a compound of formula (V) in which Y.sub.2 is a
group of formula (A.sub.2).
The aforementioned method according to the invention may also
comprise an intermediate step between step a) and step b) which
consists of purifying the compounds of formula (IV), notably on a
silica column or by distillation in a high vacuum.
For example, the monoester of formula (IV-1) is purified by using a
heptane/acetone/petroleum ether 80/10/10 mixture and the diester of
formula (IV-2) is purified by using a heptane/petroleum ether 80/20
mixture.
According to a preferred embodiment, the step b) of the method of
the invention is carried out in the presence of a peracid, this
step being notably carried out in vacuo at 200.degree. C. for less
than 3 minutes.
Among the peracids, mention may notably be made of
metachloroperbenzoic acid (m-CPBA) and magnesium
monoperoxyphthalate hexahydrate (MMPP).
The present invention also relates to a method for preparing a diol
as defined above, in which, when the compound of formula (IV) is a
compound in which Y.sub.2 is a group of formula (A.sub.2), the
epoxidation step b) is carried out in the presence of
H.sub.2O.sub.2 and of formic acid or in the presence of
H.sub.2O.sub.2 and acetic acid.
The aforementioned method according to the invention may also
comprise an intermediate step between step b) and step c) which
consists of purifying the compounds of formula (V), notably on a
silica column.
However, this purification step is optional, given that the
compounds of formula (V) may also be used directly without being
purified.
For example, the monoester of formula (V-1) is purified by using a
toluene/ethyl acetate 60/40 mixture and the diester of formula
(V-2) is purified by using a toluene/ethyl acetate 95/5
mixture.
According to a preferred embodiment, the preparation method
according to the invention is characterized in that step c) is
carried out in the presence of a catalyst selected from the group
consisting of an acid catalyst of the proton ion exchange resin
type, notably with sulfonic acid functions (resin Amberlyst.RTM. 15
Dry), heterogeneous catalysts, of para-toluenesulfonic acid (PTSA)
or of methanesulfonic acid (MSA) at a temperature comprised between
from 20.degree. C. to 120.degree. C., preferably at 70.degree.
C.
The aforementioned method according to the invention may also
comprise an additional step consisting, at the end of step c) of
purifying the compounds of formula (I), notably on a silica
column.
However, this purification step is optional given that the
compounds of formula (I) may also be used directly without being
purified.
For example, the compounds of formula (I) are purified by using a
toluene/ethyl acetate 40/60 mixture.
DETAILED DESCRIPTION
1. Step a): Reaction of Transesterification of the Compounds of
Formula (II') or (II)
Within the scope of the method of the invention, this
transesterification is carried out preferably from an ester of a
light alcohol (notably methanol or ethanol . . . ) of oleic
sunflower oil (compound of formula (II) or (II')) and from a diol
(compound of formula (III) or (III')) notably in the presence of
magnesium oxide as a catalyst. Several syntheses are carried out
with different diols in order to modulate the properties of the
monomers and therefore of the resulting polymers.
Transesterifications were therefore carried out from propanediol,
hexanediol, butanediol and hydroxyl telechelic
poly(ethyleneoxide).
The reaction takes place between 150.degree. C. and 200.degree. C.
under nitrogen flow. The progression of the reaction is tracked by
different analyses and notably MNR (disappearance of the singlet of
the methyl group). Depending on the reaction conditions, two
products are obtained:
If the diol used is placed in a great excess, in majority at least
80%, or even 95% of monoesters (or derivatives of monoglycerides)
are obtained having a terminal hydroxyl group. This alcohol at the
end of the chain then provides a first functionality to the
monomer.
Conversely, if the diol is voluntarily introduced in default, in
majority at least 60%, or even 85% of diesters (or derivatives of
diglycerides) are obtained. This second precursor then exactly has
two double bonds through which will be introduced the hydroxyl
groups, allowing access to monomers with a functionality equal to
two.
TABLE-US-00001 Reaction time Yield Alcohols used Synthesis of
Synthesis of Synthesis of Synthesis (II) or (II') monoesters
diesters monoesters of diesters Propanediol 10 h 15 h 80% 62%
Hexanediol 10 h 15 h 80% 60% Polyoxyethylene 15 h 20 h 75% 59%
(M.sub.w = 300 g/mol) Polyoxyethylene 15 h 20 h 75% 59% (M.sub.w =
600 g/mol)
Step a) (with R.sub.1.dbd.C.sub.6H.sub.13; A.sub.1=C.sub.9H.sub.18,
R.sub.2.dbd.CH.sub.3; A.sub.2=R) may thus notably be illustrated by
the following diagram:
##STR00042##
The prepared synthons (corresponding to the compounds of formula
(IV)) are for example purified on a silica column with a
heptane/acetone/petroleum ether 80/10/10 mixture for the monoester
and a heptane/petroleum ether 80/20 mixture for the diester. The
yields after purification are given in the table above.
At the end of this first step, two precursors are available: the
first is a monoester (compound of formula (IV-1)) having a terminal
hydroxyl group and a double bond on the chain; the second one is a
diester (compound of formula (IV-2)) exactly having two double
bonds in order to obtain subsequently a symmetrical polyol
containing two hydroxyl groups. The synthesis route set into play
is <<clean>> since it resorts to heterogeneous
catalyses (magnesium oxide) and the synthesis takes place without
any solvent. Industrial purification may be accomplished by
distillation under a high vacuum.
2. Step b): Epoxidation of the Derivatives of Monoesters and
Diesters Obtained after Transesterification
The epoxidation of fats having a primary alcohol at the end of the
chain by peracids formed in situ has never been dealt with and
cannot be achieved under the same conditions as those described
earlier. The epoxidation reaction is actually subject to
interference caused by a secondary oxidation reaction of the
terminal alcohol of the oleic sunflower monoester so as to form a
carboxylic acid. As the reagent is consumed by this secondary
reaction, epoxidation is not achieved.
Thus, a secondary esterification reaction occurs between the
catalyst (carboxylic acid) and the terminal alcohol of the
monoester according to the following scheme (specific case with
R.sub.1.dbd.C.sub.8H.sub.17 and A.sub.1=C.sub.7H.sub.14):
##STR00043##
The reduction in the amount of catalyst or of the temperature in
order to penalize the parasitic reaction nevertheless causes a
significant increase in the reaction time, and in parallel an
initial opening of the formed, fragile epoxide bridges in an acid
medium at 70.degree. C. Another epoxidation strategy without using
any reactive carboxylic acid was therefore developed by the
inventors.
The method applied within the scope of the method of the invention
for the epoxidation of a monoester with a terminal hydroxyl group
(compounds of form a (IV-1)) lies in the use of an already formed
and marketable peracid, i.e. notably metachloroperbenzoic acid
(m-CPBA), and therefore avoids the use of potentially toxic
metals.
The mechanism of this reaction may be illustrated according to the
scheme hereafter:
##STR00044##
Within the scope of the invention, epoxidation was achieved with
peracids (mCPBA, MMPP . . . ). The reaction may be tracked by MNR;
the disappearance of the proton doublets of the double bond at 5.2
ppm as well as the appearance of a broad peak at 2.8 ppm allows
tracking of the progression of the reaction. The conversion of the
double bonds is total after 3 h. The excess m-CPBA is reduced into
the corresponding carboxylic acid with a saturated solution of
sodium sulfate. The organic phase is extracted with dichloromethane
and then the residual carboxylic acid is transformed into
sodiumchlorobenzoate (soluble in water) by means of two washings
with a saturated solution of sodium bicarbonate.
The diesters (compounds of formula (IV-2)), not having any hydroxyl
groups, may be epoxidized by using the standard procedure
(H.sub.2O.sub.2+formic acid) or by using a peracid as indicated
above, for example metachloroperbenzoic acid.
The obtained synthons are all purified on a silica column with a
toluene/ethyl acetate 60/40 mixture for the epoxidized monoester
and a toluene/ethyl acetate 95/5 mixture for the epoxidized
diester.
3. Step c): Opening the Epoxides of the Monoesters and Diesters
Epoxidized by Alcohols
Within the scope of the present invention, the goal is to introduce
hydroxyl groups on monoesters already having a terminal primary
alcohol by opening the epoxides with an alcohol.
At 110.degree. C. and under acid catalyses (p-toluenesulfonic
acid), transesterification is favored as compared to the opening of
the epoxide. Indeed, the primary alcohol at the end of the chain is
set into play in these secondary reactions.
For example the formation of couplings is observed upon opening the
epoxide notably according to the following scheme:
##STR00045##
Tests conducted at lower temperatures show that the couplings are
reduced but the opening of the epoxide is considerably slowed down.
Many openings of epoxides use homogeneous acid catalysts (U.S. Pat.
No. 4,508,853; Gruber et al., Fett Wissenschaft Technologie, 1987,
4:147-151; EP 0 260 499; U.S. Pat. No. 4,742,087; DE 4 232 167; Guo
et al., J. Polym. Sci. A: Polym. Chem., 2000, 38: 3900-3910; U.S.
Pat. No. 6,433,121; U.S. Pat. No. 6,573,354; Zlatanic et al., J.
Polym. Sci. B: Polym. Physics, 2004, 42: 809-819; US 20070232816)
or amines (DE 4 238 215).
The method of the present invention consists of using a specific
catalyst upon opening the epoxide and operational at lower
temperatures in order not to trigger a beginning of
transesterification.
The reaction conditions applied for step c) of the method of the
invention are milder than with conventional homogeneous catalyses
(70.degree. C. instead of 110.degree. C.) and the synthesis is
accomplished without any solvent. Thus, the epoxidized monoesters
and diesters are mixed with a large excess of alcohol in the
presence of 4% by mass of resin Amberlyst 15 Dry. The medium is
heated to 70.degree. C. for 15 h. The progression of the reaction
is tracked by MNR by the disappearance of the peaks of the epoxide
at 2.8 ppm. The mixture is then filtered in order to recover the
catalyst.
The alcoholized synthons are then purified on a silica column with
a toluene/ethyl acetate 40/60 mixture for the hydroxylated
monoesters and diesters.
The present invention also relates to a compound fitting the
following general formula (I''):
##STR00046##
wherein: R'.sub.1 represents H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally be substituted with one or more groups OR.sub.a, R.sub.a
representing H or a group R' as defined below, A.sub.1 represents a
linear or branched divalent alkylene radical, comprising from 2 to
14 carbon atoms, R'' represents: a linear or branched alkyl group
R' comprising from 1 to 18 carbon atoms, or a group of formula
-A.sub.2-OH, A.sub.2 representing a linear or branched divalent
alkylene radical, comprising from 1 to 10 carbon atoms, if
necessary comprising one or more substituents, notably selected
from the group consisting of the phenylene radical and of the
radical of formula --(CH.sub.2OCH.sub.2).sub.n-- n representing an
integer comprised from 1 to 100, preferably from 6 to 50, and
preferentially equal to 6, 13 or 45, A.sub.2 preferably
representing a radical of formula --CH.sub.2-A.sub.3-CH.sub.2--,
A.sub.3 representing a group of formula
--(CH.sub.2OCH.sub.2).sub.n--, n representing an integer comprised
from 1 to 100, and preferably equal to 6, 13 or 45, or a phenylene
radical, and R.sub.3 represents: a linear or branched alkyl group
R.sub.2, comprising from 1 to 10, preferably from 1 to 6 carbon
atoms, or a group of formula -A.sub.2O--Y', A.sub.2 being as
defined above and Y' representing a hydrogen atom or a group of
formula (A')
##STR00047## A.sub.1, R' and R'.sub.1 being as defined above in
formula (I''),
it being understood that when R'' is a group R' then R.sub.3
represents a group of formula -A.sub.2-O--Y', and that when R'' is
a group -A.sub.2-OH then R.sub.3 represents a group R.sub.2.
The present invention also relates to a compound fitting the
following general formula (I''-1):
##STR00048##
wherein: R'.sub.1 represents H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally be substituted with one or more groups OR.sub.a, R.sub.a
representing H or a group R' as defined below, A.sub.1 represents a
linear or branched divalent alkylene radical, comprising from 2 to
14 carbon atoms, A.sub.2 represents a linear or branched divalent
alkylene radical, comprising from 1 to 10 carbon atoms, if
necessary comprising one or more substituents, notably selected
from the group consisting of the phenylene radical and of the
radical of formula --(CH.sub.2OCH.sub.2).sub.n--, n representing an
integer comprised between from 1 to 100, preferably from 6 to 50,
and preferentially equal to 6, 13 or 45, A.sub.2 preferably
representing a radical of formula --CH.sub.2-A.sub.3-CH.sub.2--,
A.sub.3 representing a group of formula
--(CH.sub.2OCH.sub.2).sub.n--, n representing an integer comprised
from between 1 to 100, and preferably equal to 6, 13 or 45, or a
phenylene radical, and R.sub.2 represents a linear or branched
alkyl group, comprising from 1 to 10, preferably from 1 to 6 carbon
atoms.
The present invention also relates to a compound fitting the
following general formula (I'):
##STR00049##
wherein:
R'.sub.1 represents H or a linear or branched alkyl group,
comprising from 2 to 14 carbon atoms, said alkyl group may
optionally be substituted with one or more groups OR.sub.a, R.sub.a
representing H or a group R' as defined below,
R' represents a linear or branched alkyl group, comprising from 1
to 18 carbon atoms,
A.sub.1 represents a linear or branched divalent alkylene radical,
comprising from 2 to 14 carbon atoms,
A.sub.2 represents a linear or branched divalent alkylene radical,
comprising from 1 to 10 carbon atoms, if necessary comprising one
or more substituents, notably selected from the group consisting of
the phenylene radical and of the radical of formula
--(CH.sub.2OCH.sub.2).sub.n--, n representing an integer comprised
between from 1 to 100, and preferably equal to 6, 13 or 45,
Y' represents a hydrogen atom or a group of formula (A')
##STR00050##
A.sub.1, R' and R'.sub.1 being as defined above in formula
(I').
Among the aforementioned preferred compounds, mention may notably
be made of the compounds of the following formula (I):
##STR00051##
wherein:
R.sub.1 represents a linear or branched alkyl group, comprising
from 2 to 14 carbon atoms, and
R', A.sub.1 and A.sub.2 are as defined above in formula (I'),
and
Y represents a hydrogen atom or a group of formula (A)
##STR00052##
A.sub.1, R' and R.sub.1 are as defined above in formula (I).
Mention may also be made of other preferred compounds according to
the present invention, fitting the following general formula
(I-1):
##STR00053##
wherein:
R.sub.1, R', A.sub.1 and A.sub.2 are as defined above in formula
(I') and (I).
The present invention also relates to compounds fitting the
following general formula (I''-1-1):
##STR00054##
wherein:
m, n, p and q are integers comprised between from 1 to 18, m being
preferably equal to 2.
Preferably, in formula (I''-1-1), q is equal to 4.
The present invention also relates to compounds fitting the
following general formula (I-1-1):
##STR00055##
wherein:
m, n and p are integers comprised between from 1 to 18,
and R' is as defined above in formula (I').
The present invention also relates to compounds fitting the
following general formula (I-1-2):
##STR00056##
Another family of preferred compounds of the invention consists of
the compounds fitting the following general formula (I-2):
##STR00057##
wherein:
R.sub.1, R', A.sub.1 and A.sub.2 are as defined above in formulae
(I') and (I).
Another family of preferred compounds of the invention consists of
compounds fitting the following general formula (I-2-1):
##STR00058##
wherein:
m, n and p are integers comprised between from 1 to 18,
and R' is as defined above in formula (I').
Another family of preferred compounds of the invention consists of
the compounds fitting the following general formula (I-2-2):
##STR00059##
m being as defined above.
Among the preferred polyols of the invention, mention may notably
be made of the two following specific compounds: a diol (8) derived
from sunflower oil:
##STR00060## a diol (11) derived from rape seed oil:
##STR00061##
The polyols according to the present invention, notably the diols,
have the specificity of being well defined, with two primary or
secondary hydroxyl groups. The derivatives of diesters are original
because of their symmetry and the alcohol used for
transesterification gives the possibility of varying the structure
of the synthons and thus the properties of the resulting
polymers.
The diols obtained by these different methods may then be used
inter alia as monomers. Their purity allows optimization of the
properties of the obtained polymers.
Thus, polyurethanes were then synthesized by bulk polymerization of
these polyols with IPDI (or for example also with MDI, HMDI or
HDI), at 60.degree. C. in the presence of tin dibutyl dilaurate.
Formation of the polyurethanes is confirmed by FTIR with the
disappearance of the vibration band of the isocyanate. Steric
exclusion chromatography confirms molar masses comprise between 14
000 and 50 000 g/mol. These di-OH monomers may also be used for the
synthesis of other polymers such as polyesters, polyethers,
polycarbonates, etc.
The polyol compounds according to the present invention of formula
(I), (I') or (I'') are notably used for reacting with
polyisocyanates in order to form polyurethanes.
Thus, these compounds may be used for preparing rigid foams, of
electric insulators, of coatings, of adhesives, of flexible foams
(notably in the field of furniture or of automobiles) or of shoe
soles.
More exactly, the polyols according to the present invention are
used for preparing rigid foams by reacting them with
polyisocyanates in the presence of a catalyst and of a foaming
agent (to which may also be added surfactants, coloring agents,
antioxidants, preservatives, plasticizers, cross-linking agents,
flame retardants, etc.).
Preferably, such a rigid foam may be prepared by reacting together
the following constituents: 60 g of polyisocyanate, 40 g of polyol,
1.2 g of water (foaming agent), 0.1-0.4 g of catalyst and 1-4 g of
surfactant.
More exactly, the polyols according to the invention are used for
preparing electric insulators by reacting them with polyisocyanates
in the presence of an anti foaming agent and of a drying agent.
Preferably, such an electric insulator may be prepared by reacting
together 60 g of polyol, 29 g of polyisocyanate, 0.6 g of anti
foaming agent and 3 g of drying agent, and optionally 60 g of
fillers (silica).
More exactly, the polyols according to the invention are used for
preparing coatings by reacting them with polyisocyanates. For
example, coatings are prepared by using pure polyols and
polyisocyanates, or by using polyols and polyisocyanates with
solvents (it is also possible to add coloring agents, pigments,
fillers, flow additives, anti oxidants, bactericides, fungicides,
corrosion inhibitors, catalysts or UV stabilizers).
For the preparation of adhesives according to the present
invention, provision is also made for using pure polyols of the
invention with pure polyisocyanates.
As regards flexible foams, preferably 60 g of polyol according to
the invention, 100 g of isocyanate, 4.5 g of water (foaming agent),
0.12 g of catalyst 1, 0.38 g of catalyst 2 and 3 g of surfactant
are used.
Finally, a specific formulation according to the invention for
preparing shoe soles comprises 59 g of isocyanate, 94.5 g of polyol
according to the invention, 4.1 g of ethylene glycol and 1.4 of
catalyst.
The present invention also relates to the intermediate compounds
fitting one of the following formulae:
##STR00062##
R''.sub.1, A.sub.1, A.sub.2, Y.sub.1, Y'.sub.1, R.sub.2, R.sub.4
and R.sub.1 are as defined above in formula (I), (I') and
(I'').
The present invention also relates to the intermediate compounds
fitting one of the following formulae:
##STR00063##
R''.sub.1, A.sub.1, A.sub.2, Y.sub.2, Y'.sub.2, R.sub.5, R.sub.2
and R.sub.1 are as defined above in formulae (I) and (I').
A particularly preferred family of intermediate compounds according
to present invention consists of compounds fitting the following
formula (V-3):
##STR00064##
A.sub.1 and A.sub.2 are as defined above in formula (I'), and
A.sub.1 preferably representing a group C.sub.7H.sub.14.
The present invention therefore also relates to the synthesis of
bis-epoxide precursors, notably for epoxy resins.
These bis-epoxide precursors have two terminal epoxide groups and
are close to the structure of bisphenol A diclycidyl ether (BADGE).
BADGE is widely used as a precursor in the synthesis of epoxy
resin, by a condensation reaction with diamines. However BADGE is
in the process of being banned because of the toxicity of its
bisphenol A. The bis-epoxides according to the invention of the
aforementioned formula (V-3) prove to be an alternative to the use
of BADGE.
The literature already describes the use of vegetable oil in the
formulation of epoxy resins: epoxidised sunflower oil (Jiang Zhu et
al., Journal of Applied Polymer Science, 2004, 91, 3513-3518),
epoxidized castor oil (Park et al., Macromolecular Chemistry and
Physics, 2004, 205, 2048-2054) or carbonated soya bean oil
(Parzuchowski et al., Journal of Applied Polymer Science, 2006,
102, 2904-2914). Nevertheless these oils only replace a small
proportion of BADGE because of their low reactivity. The attained
epoxy resins have equivalent mechanical properties or even superior
to commercial epoxy resins from petroleum. For the moment, a
maximum of 30% of epoxidized oil has been incorporated into
commercial resins. With the mixture of epoxidized flax oil, of
bisphenol F diglycidyl ether (BFDGE), and of an anhydride adjuvant,
it is possible to obtain resins containing up to 70% of epoxidized
flax oil (Miyagawa et al., Marcomoecular Materials and Engineering,
2004, 289, 629-635).
The synthesis of epoxy resins from 100% of vegetable oil is not
possible because of the low reactivity of the internal epoxide
groups in the chain. The synthesis route proposed within the scope
of the present invention gives the possibility of obtaining
precursors having two terminal epoxide groups, which increases the
reactivity towards amines and allows the synthesis of epoxy resins
from 100% of vegetable oil.
The method for preparing the compounds of formula (V-3) may be
illustrated by the diagram hereafter:
##STR00065##
Preferably A.sub.1 represents a radical C.sub.7H.sub.14.
The present invention also relates to polymers of the polyurethane
type as obtained by polymerization of the polyols of the present
invention, notably of formulae (I''), (I') or (I), with
(poly)isocyanates.
It also relates to polymers of the polyester type as obtained by
polymerization of the polyols of the present invention, notably of
formulae (I''), (I') or (I).
EXPERIMENTAL PART
Example 1
Preparation of Oleic Sunflower Oil Ethyl Esters
This example relates to the preparation of the compound (1) of the
following formula:
##STR00066##
This is a compound of formula (II) in which R.sub.1 represents an
alkyl group comprising 8 carbon atoms, A.sub.1 represents an
alkylene radical comprising 7 carbon atoms and R.sub.2 represents
an ethyl group.
The starting product is oleic sunflower oil (OSO) of formula:
##STR00067##
In a jacketed reactor are introduced 604.8 g of oleic sunflower oil
(OSO) (ITERG, M=884.82 gmol.sup.-1-water content=0.35% by weight)
with 188.2 g of absolute ethanol (JT Baker-M=46.07 gmol.sup.-1).
The whole is mixed with stirring at 650 rpm.sup.-1 and heated to
65.degree. C. 6.7211 g of MeONa (Aldrich-M=54.02 gmol.sup.-1) are
then added into the reactor and a change in color of the product
and the appearance of instantaneous turbidity are then noticed. The
whole was then left to react for 1 h at 70.degree. C.
The resulting reaction mixture was then transferred into a
separating funnel in order to remove the glycerol and evaporate the
ethanol. Neutralization was then carried out with a few drops of
HCl and then washing with water until neutrality. Finally, the
residual water was distilled in the Rotavapor.
532.1 g of sunflower oil ethyl ester of the aforementioned formula
(1) were obtained with a water content of 0.35% by weight.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained comprising 98.2% by
weight of ethyl ester.
Example 1bis
Preparation of Oleic Sunflower Oil Ethyl Esters
This example relates to the preparation of compound (1) of the
aforementioned Example 1 from oleic sunflower oil (OSO).
In a jacketed reactor are introduced 502.8 g of oleic sunflower oil
(OSO) (ITERG) with 161.5 g of absolute ethanol (JT Baker-M=46.07
gmol.sup.-1). The whole is mixed with stirring at 650 rpm.sup.-1
and heated to 65.degree. C. 5.5880 g of MeONa (Aldrich-M=54.02
gmol.sup.-1) are then added into the reactor and a change in color
of the product and the appearance of instantaneous turbidity are
then noticed. The whole is then left to react for 5 h at 70.degree.
C.
The resulting reaction mixture was then transferred into a
separating funnel in order to remove the glycerol and evaporate the
ethanol. Neutralization was then carried out with a few drops of
HCl and then washing with water until neutrality. Finally, the
residual water was distilled in the Rotavapor.
455.2 g of sunflower oil ethyl ester of the aforementioned formula
(1) was thereby obtained with a water content of 0.29% by
weight.
According to characterization by gas phase chromatography which was
carried out, a composition was obtained comprising 97.4% by weight
of ethyl ester.
Example 2
Preparation of Oleic Sunflower Oil Butanediol Esters
This example relates to the preparation of the compound (2) of the
following formula:
##STR00068##
This is a compound of formula (IV) in which R.sub.1 represents an
alkyl group comprising 8 carbon atoms, A.sub.1 represents an
alkylene radical comprising 7 carbon atoms, A.sub.2 represents a
butylene radical and Y.sub.1 represents H or a group of formula
(A.sub.1) as defined above.
The starting product is the compound (1) as obtained in Example
1.
In a reactor (500 mL) are introduced 301.5 g of compound (1)
(OSOEE) with 43.1 g (0.5 mol) of 1,4-butanediol (Aldrich) (compound
of formula (III) with A.sub.2=butylenes). The whole is heated to
65.degree. C. 3.3602 g of MeONa (Aldrich) are then added into the
reactor and a change in color of the product (opaque yellow) is
then noticed. The whole is then left to react for 6 hours at
70-75.degree. C. with stirring (650 rpm.sup.-1) at a pressure from
800 to 300 mbars.
Neutralization was then carried out with few drops of HCl and then
with washing with water in order to remove the traces of butanediol
until neutrality. Finally the residual water was distilled in the
Rotavapor.
279 g of sunflower oil butanediol ester of the aforementioned
formula (2) were thereby obtained with a water content of 0.22% by
weight. The product of formula (2) is in the form of a limpid
yellow liquid and has an acid index of 3.58%.
According to characterization by gas phase chromatography which was
carried out, a composition was obtained comprising:
after 1 hour: 70% by weight of diesters (compound (2) with
Y.sub.1=(A.sub.1)), 11.1% by weight of monoesters (compound (2)
with Y.sub.1.dbd.H) and 18.9% of compound (1).
after 7 hours: 74.5% by weight of diesters (compound (2) with
Y.sub.1=(A.sub.1)), 12.5% by weight of monoesters (compound (2)
with Y.sub.1.dbd.H) and 16% of compound (1).
Moreover, with additional purifications it was possible to increase
the yield and notably obtain up to 85% by weight of diesters, and
this by carrying out distillation of the residual monoesters.
Example 3
Preparation of Oleic Sunflower Oil Epoxidized Butanediol Esters
This example relates to the preparation of the compound (3) of the
following formula:
##STR00069##
This is a compound of formula (V) in which R.sub.1 represents an
alkyl group comprising 8 carbon atoms, A.sub.1 represents an
alkylene radical comprising 7 carbon atoms, A.sub.2 represents a
butylenes radical and Y.sub.2 represents H or a group of formula
(A.sub.2) as defined above.
The starting product is the compound (2) as obtained in Example 2
having the following composition: 83.7% by weight of diesters,
8.80% by weight of monoesters and 7.50% by weight of ethyl ester
(compound (1)).
In a reactor (250 mL) are introduced 79.7 g of compound (2)
butanediol esters) with 7 g (0.3 mol) of formic acid HCOOH (BAKER)
at 45.degree. C. for 1 hour at 500 rpm.sup.-1. Hydrogen peroxide
was then added with a dropping funnel dropwise for 10 minutes (36.7
g (2 moles) of 50% H.sub.2O.sub.2 (BAKER)). The whole was then left
to react for 2 hours at 75.degree. C. with stirring at 650
rpm.sup.-1. As the reaction is exothermic, the medium was cooled
with a bath of cold water.
Washing with water was then carried out until neutrality of the
washing waters. Finally, the residual water was distilled in the
Rotavapor.
79.3 g of sunflower oil epoxidized butanediol esters of the
aforementioned formula (3) were thereby obtained. The product of
formula (3) is in the form of a white solid at room temperature and
has an acid index of 1.95%.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained comprising 86.8% by
weight of diesters (compound (3) with Y.sub.2=(A.sub.2))) 7.3% by
weight of monoesters (compound (3) with Y.sub.2.dbd.H) and 5.9% by
weight of compound (1).
Example 4
Preparation of the Diol (4)
This example relates to the preparation of the compound (4) of the
following formula:
##STR00070##
This is a compound of formula (I) in which R.sub.1 represents an
alkyl group comprising 8 carbon atoms, A.sub.1 represents an
alkylene radical comprising 7 carbon atoms, A.sub.2 represents a
butylene radical, R' represents an ethyl group and Y represents H
or a group of formula (A) as defined above.
The starting product is the compound (3) as obtained in Example 3
having the following composition: 86.8% by weight of diesters, 7.3%
by weight of monoesters and 5.9% by weight of ethyl ester (compound
(1)).
In a reactor (250 mL) are introduced 60.2 g of compound (3)
(butanediol epoxidized esters) with 2.4 g (4% by weight) of
Amberlyst (Aldrich) resin and 112.6 g (15 moles) of absolute
ethanol (BAKER). The whole was left to react at 70.degree. C. for 4
hours at 500 rpm. The resin was then filtered on a Buchner and
finally the residual ethanol was distilled in the Rotavapor.
53.6 g of the polyol of the aforementioned formula (4) were thereby
obtained. The product of formula (3) is in the form of a pale
yellow liquid and has an acid index of 1.37%.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained comprising less than
0.5% by weight of butanediol, 82.0% by weight of diesters (compound
(1) with Y=(A)), 7.6% by weight of monoesters (compound (1) with
Y.dbd.H) and 10.4% by weight of compound (1).
The compound (4) was analyzed by IR spectroscopy and an OH band was
observed at 3 461.76 cm.sup.-1 and a secondary alcohol band at 1
087.24 cm.sup.-1.
Example 5
Preparation of Castor Oil Ethyl Esters
This example relates to the preparation of the compound (5) of the
following formula:
##STR00071##
This is a compound of formula (II') in which R''.sub.1 represents
an alkyl group comprising 8 carbon atoms and substituted with an OH
group (on the carbon 7), A.sub.1 represents an alkylene radical
comprising 7 carbon atoms and R.sub.2 represents an ethyl
group.
The starting product is castor oil with the formula:
##STR00072##
In a jacketed reactor (1 liter) were introduced 402.4 g of castor
oil (ITERG, M=928 gmol.sup.-1-water content=0.35% by weight) with
405.4 g of absolute ethanol (JT Baker-M=46.07 gmol.sup.-1). The
whole is mixed with stirring at 650 rpm.sup.-1 and heated to
65.degree. C. 4.5214 g of MeONa (Aldrich-M=54.02 gmol.sup.-1) are
then added into the reactor and a change in color of the product
and the appearance of instantaneous turbidity are then noticed. The
whole is left to react for 30 minutes at 50.degree. C.
The resulting reaction mixture was then transferred into a
separating funnel in order to remove the glycerol and evaporate the
ethanol. Neutralization was then carried out with a few drops of
HCl and then washing with water until neutrality. Finally, the
residual water was distilled in the Rotavapor.
360.2 g of castor oil ethyl ester of the aforementioned formula (5)
were thereby obtained with a water content of 0.23% by weight.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained comprising 93.8% by
weight of ethyl ester.
Example 6
Preparation of Castor Oil Butanediol Esters
This example relates to the preparation of the compound (6) of the
following
##STR00073##
This is a compound of formula (IV') in which R''.sub.1 represents
an alkyl group comprising 8 carbon atoms and substituted with an OH
group (on the carbon 7), A.sub.1 represents an alkylene radical
comprising 7 carbon atoms, A.sub.2 represents a butylenes radical
and Y'.sub.1 represents H or a group of formula (A'.sub.1) as
defined above.
The starting product is the compound (5) as obtained in Example
5.
In a reactor (500 mL) are introduced 300.5 g of compound (5) with
43.5 g (0.5 mol) of 1,4-butanediol (Aldrich) (compound of formula
(III) with A.sub.2=butylene). The whole is heated to 65.degree. C.
3.6005 g of MeONa (Aldrich) are then added into the reactor and a
change in color of the product (opaque yellow) was then noticed.
The whole is then left to react for 6 hours at 70-75.degree. C.
with stirring (650 rpm.sup.-1) at a pressure from 800 to 2
mbars.
Neutralization was then carried out with a few drops of HCl and
then washing with water in order to remove the butanediol traces
until neutrality. Finally, the residual water was distilled in the
Rotavapor.
260 g of castor oil butanediol ester of the aforementioned formula
(6) were thereby obtained with a water content of 0.30% by weight.
The product of formula (6) is in the form of a yellow liquid and
has an acid index of 5.05%.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained comprising 43.9% by
weight of diesters (compound (6) with Y'.sub.1=(A'.sub.1)), 30.4%
by weight of monoesters (compound (6) with Y'.sub.1.dbd.H) and
25.7% by weight of compound (5).
Example 7
Preparation of Epoxidized Sunflower Oil Ethyl Esters
This example relates to the preparation of the compound (7) of the
following
##STR00074##
This is a compound of formula (IV''-2) in which R.sub.1 represents
an alkyl group comprising 8 carbon atoms, A.sub.1 represents an
alkylene radical comprising 7 carbon atoms and R.sub.2 represents
an ethyl group.
The starting product is the oleic sunflower oil ethyl ester
compound of Example 1bis.
In a reactor (1 L) are introduced 399.6 g of the compound (1) of
Example 1 bis (oleic sunflower oil ethyl ester--OSOEE) and 20.1 g
of formic acid and the whole was left to react at 45.degree. C. for
1 hour at 500 rpm.sup.-1. Next hydrogen peroxide was added dropwise
with a dropping funnel for 40 minutes (199.2 of H.sub.2O.sub.2
(BAKER)). The whole was then left to react for 2 hours at
75.degree. C. with stirring at 650 rpm.sup.-1. As the reaction is
exothermic, the medium was cooled with a cold water bath.
Washing with water was then carried out until neutrality of the
washing waters. Finally, the residual water was distilled in the
Rotavapor.
410.3 g of oleic sunflower oil epoxidized ethyl esters of the
aforementioned formula (7) were thereby obtained. The product of
formula (7) is in the form of an orangey liquid and has an acid
index of 0.79%, as well as a water content of 0.41%.
Example 8
Preparation of the Diol (8)
This example relates to the preparation of the compound (8) of the
following
##STR00075##
This is a compound of formula (I''-1) in which R'.sub.1 represents
an alkyl group comprising 8 carbon atoms, A.sub.2 represents a
butylene radical, A.sub.1 represents an alkylene radical comprising
7 carbon atoms and R.sub.2 represents an ethyl group.
The starting product is the epoxidized oleic sunflower oil ethyl
ester compound of Example 7.
In a reactor (2 L) 301.2 g of compound (7) are introduced with 12 g
(4% by weight) of Amberlyst resin (Aldrich) and 1 201.1 g of
distilled 1,4-butanediol (Aldrich). The whole as left to react at
70.degree. C. for 4 hours at 500 rpm.sup.-1.
The butanediol was distilled at 120-150.degree. C. under 30 mbars
and the whole was washed with water for removing the traces of
butanediol. The resin was then filtered on a Buchner and, finally
the residual ethanol was distilled in the Rotavapor.
270.3 g of the polyol of the aforementioned formula (8) were
thereby obtained. The product of formula (8) has an acid index of
0.27% and a hydroxyl index of 255.8 mg KOH/g.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained, comprising less than
0.1% by weight of butanediol, 22% by weight of diesters, 71.7% by
weight of monoesters (compound 8) and 6.1% by weight of compound
(1).
Example 9
Preparation of Erucic Rape Seed Oil Ethyl Esters
This example relates to the preparation of the compound (9) of the
following
##STR00076##
This is a compound of formula (II) in which R.sub.1 represents an
alkyl group comprising 12 carbon atoms, A.sub.1 represents an
alkylene radical comprising 7 carbon atoms and R.sub.2 represents
an ethyl group.
The starting product is erucic rape seed oil of formula:
##STR00077##
In a jacketed reactor (1.5 liter) are introduced 1 004.7 g of
erucic rape seed oil (ERO) (ITERG, M=951.8 gmol.sup.-1-water
content=0.35% by weight) with 290.7 of absolute ethanol (JT
Baker-M=46.07 gmol.sup.-1). The whole is mixed with stirring at 650
rpm.sup.-1 and heated to 65.degree. C. 11.1 g of MeONa
(Aldrich-M=54.02 gmol.sup.-1) were then added into the reactor and
a change in the color of the product and the appearance of
instantaneous turbidity was then noticed. The whole is then left to
react for 1 hour at 70.degree. C.
The resulting reaction mixture was then transferred into a
separating funnel in order to remove the glycerol and evaporate the
ethanol. Neutralization was then carried out with a few drops of
HCl and then washing with water until neutrality. Finally the
residual water was distilled in the Rotavapor.
1 026.8 g of rape seed oil ethyl ester of the aforementioned
formula (9) of the were thereby obtained with a water content of
0.27% by weight and an acid index of 1.04%.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained comprising 98.48% by
weight of ethyl ester.
Example 10
Preparation of Epoxidized Rape Seed Oil Ethyl Esters
This example relates to the preparation of the compound (10) of the
following formula:
##STR00078##
This is a compound of formula (IV''-2) in which R.sub.1 represents
an alkyl group comprising 12 carbon atoms, A.sub.1 represents an
alkylene radical comprising 7 carbon atoms and R.sub.2 represents
an ethyl group.
The starting product is the rape seed oil ethyl ester compound of
Example 9.
In a reactor (1 L) are introduced 400.5 g of compound (9) (rape
seed oil ethyl ester--ROEE) and 23.12 g of formic acid and the
whole is left to react at 45.degree. C. for 1 hour at 500 rpm.
Hydrogen peroxide was then added dropwise with a dropping funnel
for 40 minutes (211.1 g of H.sub.2O.sub.2 (BAKER)). The whole was
then left to react for 3 hours at 75.degree. C. with stirring at
650 rpm.sup.-1. As the reaction is exothermic, the medium was
cooled with a cold water bath.
Washing with water was then carried out until neutrality of the
washing waters. Finally, the residual water was distilled in the
Rotavapor.
410.2 g of erucic castor oil epoxidized ethyl esters of the
aforementioned formula (10) were thereby obtained. The product of
formula (10) is in the form of a white solid at room temperature
and has an acid index of 1.08%, as well as a water content of
0.22%.
Example 11
Preparation of the Diol (11)
This example relates to the preparation of the compound (11) of the
following formula:
##STR00079##
This is a compound of formula (I''-1) in which R'.sub.1 represents
an alkyl group comprising 12 carbon atoms, A.sub.2 represents a
butylene radical, A.sub.1 represents an alkylene radical comprising
7 carbon atoms and R.sub.2 represents an ethyl group.
The starting product is the epoxidized erucic rape seed oil ethyl
ester compound of Example 10.
In a reactor (2 L) 350.2 g of compound (10) are introduced with
14.2 g (4% by weight) of Amberlyst resin (Aldrich) and 1 484.6 g of
distilled 1,4-butanediol (Aldrich). The whole was left to react at
70.degree. C. for 4 hours at 500 rpm.sup.-1.
Two phases were then obtained: the upper phase containing the
compound 11 and traces of butanediol and the lower phase containing
butanediol and traces of compound (11).
The upper phase was therefore distilled with magnetic stirring in
vacuo at 120-140.degree. C. under 30 mbars. The lower phase was
also distilled in vacuo and with a flow of dinitrogen without
stirring for two days in order to obtain a dark brown product.
The whole was washed with water for removing the traces of
butanediol. The resin was then filtered on a Buchner and finally
the residual ethanol was distilled in the Rotavapor.
Via the upper phase, 126 g of a pale yellow liquid were obtained
with an acid index of 0.69% and a hydroxyl index of 190.4 mg of
KOH/g, as well as a water content of 0.64%.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained comprising less than
0.1% by weight of butanediol, 6.9% by weight of diesters, 89.1% by
weight of monoesters (compound 11), 0.7% by weight of triglycerides
and 3.3% by weight of compound (9).
Via the lower phase, 135 g of a dark brown liquid were obtained
with a water content of 0.35%.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained comprising less than
0.3% by weight of butanediol, 11.4% by weight of diesters, 87.7% by
weight of monoesters (compound 11), 0.4% by weight of triglycerides
and 0.3% by weight of compound (9).
Example 12
Preparation of Polymers from Polyols of Formula (I')
By applying the same procedures as in the aforementioned examples 1
to 6, the following compounds were also synthesized:
Synthesis of Polymers from the Polyol
##STR00080##
TABLE-US-00002 Group R C.sub.3H.sub.6 C.sub.4H.sub.8
C.sub.6H.sub.12 Reaction time 5 h 5 h 5 h M.sub.w 20,000 g/mol
20,000 g/mol 18,000 g/mol IP 1.4 1.5 1.3
Synthesis of Polymers from the Polyol
##STR00081##
TABLE-US-00003 Group R C.sub.3H.sub.6 PEG.sub.300 PEG.sub.600
Reaction time 7 h 8 h 10 h M.sub.w 15,000 g/mol 14,000 g/mol 14,000
g/mol IP 1.4 1.5 1.3
The polyols of the invention are used for preparing polymers for
example by reaction with isocyanates. The applied procedure is
described hereafter and may be applied to any polyol and any
isocyanate.
In a reactor of 100 mL were added the polyol of the invention and
the catalyst and then the isocyanate (in particular IPDI) was added
into the reactor via a funnel. The temperature of the mixture was
maintained at 60.degree. C. by heating.
From the Polyol Monoester with R.dbd.O.sub.3H.sub.6
2 g of monoester were introduced into a 100 mL reactor in the
presence of 2 mg of DBTDL (LCPO) (dibutyltin dilaurate) (0.1% by
weight). And then 1.1 g of IPDI (Aldrich-M=222.29 gmol.sup.-1)
(isophorone diisocyanate) (1 equivalent) were introduced. The
mixture was placed with magnetic stirring for 5 hours.
The kinetics of the reaction were tracked by IR analysis which
allowed observation of the disappearance of the band N.dbd.C at 2
269.94 cm.sup.-1 and the appearance of the band N--H at 3 350
cm.sup.-1. The obtained polymer was analyzed by steric exclusion
chromatography (the obtained molar masses are listed in the tables
above).
The procedure is unchanged for the cases when R.dbd.C.sub.4H.sub.10
and R.dbd.O.sub.6H.sub.12.
From the Polyol Diester with R.dbd.C.sub.3H.sub.6
2 g of diester were introduced into a 100 mL reactor in the
presence of 2 mg of DBTDL (LCPO) (dibutyltin dilaurate) and then
586 mg of IPDI (Aldrich-M=222.29 gmol.sup.-1) (isophorone
diisocyanate) (0.5 equivalent) were introduced. The mixture was
placed with magnetic stirring for 7 hours.
The kinetics of the reaction were tracked by IR analysis which
allowed observation of the disappearance of the band N.dbd.C at 2
269.94 cm.sup.-1 and the appearance of the band N--H at 3 350
cm.sup.-1. The obtained polymer was obtained by steric exclusion
chromatography (the obtained molar masses are listed in the tables
above).
The procedure is unchanged for the cases when R=PEG.sub.300 and
R=PEG.sub.500.
Example 13
Preparation of Polyurethanes from the Diol 8
The polyols of the invention are used for preparing polymers for
example by reaction with isocyanates. The applied procedure is
described hereafter and may be applied to any polyol and any
isocyanate.
In a reactor of one liter, the polyol of the invention and the
catalyst were added and then the isocyanate (in particular IPDI or
HMDI) was added into the reactor via a funnel. The whole was then
stirred at 80 rpm.sup.-1 under dinitrogen in order to homogenize
the mixture. The appearance of bubbles was then observed in the
reaction mixture and the temperature of the mixture was maintained
at 60.degree. C. by heating.
The kinetics of the reaction were tracked by IR analysis which
allowed observation of the disappearance of the band N.dbd.C at 2
269.94 cm.sup.-1 and the appearance of the band N--H at 3 350
cm.sup.-1.
More particularly, this procedure was applied by using as a polyol,
the diol 8 of Example 8 and by varying the nature of the isocyanate
(IPDI and HMDI), as well as the reaction time and the OH:NCO
ratio.
The catalyst used is DBTDL (LCPO) (dibutyltin dilaurate) at 0.1% by
weight.
The obtained results are summarized hereafter in Tables 1 and
2.
TABLE-US-00004 TABLE 1 corresponds to the synthesis of polyurethane
by reaction with IPDI (Aldrich - M = 222.29 g
mol.sup.-1)(isophorone diisocyanate): Solubility Viscosity (cst)
(DCM, GPC 80.degree. C. 100.degree. C. Reaction THF, IR Analysis
Shearing (s.sup.-1) No OH:NCO time (h) DMF) Analysis (Mw) 1 10 1 10
1 1:0.2 7 soluble No isocyanate 1 830 -- 9.5 -- 4.5 band 2 1:0.3 7
soluble No isocyanate 2 300 -- 23.5 -- 11.5 band 3 1:0.5 7 soluble
No isocyanate 5 240 -- 160 -- 70 band 4 1:0.65 7 soluble No
isocyanate 10 820 1050 775 -- 280 band 5 1:0.69 12 soluble No
isocyanate 12 570 -- -- -- -- band DCM: dichloromethane THF:
tetrahydrofurane DMF: dimethylformamide The suitable viscosities
are obtained for an OH:NCO ratio of less than 1:0.70.
TABLE-US-00005 TABLE 2 corresponds to the synthesis of polyurethane
by reaction with HMDI (hexamethylene diisocyanate): Solubility
Viscosity (cst) (DCM, GPC 80.degree. C. 100.degree. C. Reaction
THF, IR Analysis Shearing (s.sup.-1) No OH:NCO time (h) DMF)
Analysis (Mw) 1 10 1 10 1 1:0.3 6 soluble No isocyanate 2 740 --
31.7 -- 14.5 band 2 1:0.5 6 soluble No isocyanate 7 200 287 385 93
188 band 3 1:0.65 9 soluble No isocyanate 13 550 3 474 3 055 879
891 band
Example 14
Preparation of a Diol of Formula (I-2) with Two Secondary Alcohol
Functions
The procedure described hereafter was used for synthesizing
compounds of formula (I-2), A.sub.1 representing a C.sub.7H.sub.14
radical and R.sub.1 representing an alkyl group comprising 9 carbon
atoms.
In formula (I-2), A.sub.2 may represent a radical selected from the
following radicals: C.sub.3H.sub.6, C.sub.4H.sub.8,
C.sub.5H.sub.10, C.sub.6H.sub.12,
H.sub.2C--(CH.sub.2OCH.sub.2).sub.6--CH.sub.2,
H.sub.2C--(CH.sub.2OCH.sub.2).sub.13--CH.sub.2,
H.sub.2C--(CH.sub.2OCH.sub.2).sub.45--CH.sub.2 or
H.sub.2C--C.sub.6H.sub.4--CH.sub.2.
Transesterification Step:
The diesters stem from transesterification of an oleic methyl ester
and of a diol (propanediol, butanediol, pentanediol, hexanediol,
polyoxyethylene (300 g/mol, 600 g/mol and 2000 g/mol)). The
synthesis involves 0.1 mol of oleic methyl ester and 0.05 mol of
diol, in the presence of magnesium oxide MgO (catalyst, 1% by mass
based on the methyl ester mass). The medium was kept with stirring
at 160.degree. C., under nitrogen flow, for 7 hours. The methanol
formed by the reaction was removed from the reaction medium by
means of a Dean Stark trap. The formation of the diester was
followed via .sup.1H MNR. After 7 hours, the medium was placed at
200.degree. C. in a dynamic vacuum for 1 hour in order to remove
the oleic methyl ester and the residual diols. The catalyst was
removed by filtration.
For the synthesis of the diester from methyl ester and
1,4-benzenedimethanol (A.sub.2=H.sub.2C--C.sub.6H.sub.4--CH.sub.2),
the temperature of the medium during the reaction was 140.degree.
C. in order not to sublimate the 1,4-benzenedimethanol.
Epoxidation Step:
10 mmol of diester synthesized previously were mixed with 3 mmol of
formic acid (HCOOH). The mixture was heated to 40.degree. C. for 1
hour. And then 10 mmol of hydrogen peroxide (H.sub.2O.sub.2) were
added dropwise. The temperature was raised to 70.degree. C. for 2
hours. The formation of the epoxide was followed by .sup.1H MNR.
When the reaction is completed, it is proceeded with
water-dichloromethane washing in order to remove the peracid.
Hydroxylation Step:
For the step for opening the epoxide, 10 mmol of epoxidized
diesters were dissolved in 100 mmol of ethanol, in the presence of
an ion exchange resin (Amberlyst 15 Dry, 4% by mass based on the
mass of the diesters). The reaction medium was placed with
stirring, at 75.degree. C. for 20 hours. The opening of the epoxide
was followed by .sup.1H MNR. When the reaction was complete, the
catalyst was removed by filtration. The excess ethanol was then
evaporated under low pressure. The hydroxylated diesters were then
analyzed with .sup.1H MNR and with steric exclusion chromatography.
Their hydroxyl index was determined.
Example 15
Preparation of a Diol of Formula (I-1) with Two Secondary Alcohol
Functions
The procedure described hereafter was used for synthesizing
compounds of formula (I-1), A.sub.1 representing a C.sub.7H.sub.14
radical and R.sub.1 representing an alkyl group comprising 9 carbon
atoms.
In the formula (I-1), A.sub.2 may represent a radical selected from
the following radicals: C.sub.3H.sub.6, C.sub.4H.sub.8,
C.sub.5H.sub.10, C.sub.6H.sub.12,
H.sub.2C--(CH.sub.2OCH.sub.2).sub.6--CH.sub.2,
H.sub.2C--(CH.sub.2OCH.sub.2).sub.13--CH.sub.2,
H.sub.2C--(CH.sub.2OCH.sub.2).sub.45--CH.sub.2 or
H.sub.2C--C.sub.6H.sub.4--CH.sub.2.
The synthesis procedures are the same as those indicated for
example 14, except for the transesterification step. The synthesis
involves 0.1 mol of oleic methyl ester and 1.5 mol of diol, in
order to promote formation of monoesters relatively to
diesters.
Example 16
Preparation of Bisepoxide Compounds of Formula (V-3)
##STR00082##
The first step consisted of cutting the carbonaceous chain of the
oleic methyl ester at the internal double bond in order to obtain
an internal double bond. A metathesis reaction between ethylene and
the internal double bond of the oleic methyl ester in the presence
of Hoveyda catalyst lead to the formation of decene and of methyl
10-undecenoate. This reaction took place with stirring at room
temperature. In the equilibrium state, the medium consists of 48%
of initial oleic methyl ester, 26% of decene and 26% of methyl
10-undecenoate. The latter was extracted by distillation in vacuo:
the first fraction at 100.degree. C. contained decene; methyl
10-undecenoate was recovered when the temperature reached
180.degree. C. The residue consisted of oleic methyl ester.
It was then proceeded with a reaction for transesterification of
methyl 10-undecenoate with a diol (aliphatic, aromatic diol, phenol
of natural origin, etc.). The reaction took place in vacuo in the
presence of 0.5 equivalent of diol in order to promote formation of
diesters; it was catalyzed with 1 wt % of magnesium oxide. The
temperature of the medium was raised to 160.degree. C., the
produced methanol was removed continuously by means of a Dean Stark
trap. After 7 hours, the temperature was raised to 180.degree. C.
in order to remove the residual methyl 10-undecenoate.
The last step consisted in the epoxidation of the double bonds of
the product obtained by transesterification. It was carried out in
the presence of metachloroperbenzoic acid (m-CPBA) (1.2 equiv. per
double bond), in dichloromethane at room temperature. The
conversion of the double bonds was total after 3 hours. The excess
m-CPBA was reduced into the corresponding carboxylic acid with a
saturated solution of sodium sulfate. The organic phase was
extracted with dichloromethane and then the residual carboxylic
acid was transformed into sodium chlorobenzoate (soluble in water)
by two washings with a saturated solution of sodium
bicarbonate.
Example 17
Preparation of Oleic Sunflower Oil Ethyl Esters
This example relates to the preparation of the compound (1) of the
aforementioned Example 1 from oleic sunflower oil (OSO).
In a jacketed reactor are introduced 1 001.2 g of oleic sunflower
oil (OSO) (ITERG, M=884.82 gmol.sup.-1-water content=0.35% by
weight) with 314.0 g of absolute ethanol (JT Baker-M=46.07
gmol.sup.-1). The whole is mixed with stirring at 650 rpm.sup.-1
and heated to 65.degree. C. 11.5 g of MeONa (Aldrich-M=54.02
gmol.sup.-1) were then added into the reactor and a change in color
of the product and the appearance of instantaneous turbidity were
then noticed. The whole was then left to react for 1 hour at
70.degree. C.
The resulting reaction mixture was then transferred into a
separating funnel in order to remove the glycerol and evaporate the
ethanol. Neutralization was then carried out with a few drops of
HCl and then washing with water until neutrality. Finally, the
residual water was distilled in the Rotavapor.
1 056.5 g of sunflower oil ethyl ester of the aforementioned
formula (1) with a water content of 0.15% by weight were thereby
obtained.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained comprising 97.8% by
weight of ethyl ester.
Example 18
Preparation of Epoxidized Sunflower Oil Ethyl Esters
This example relates to the preparation of the compound (7) of
Example 7 from the compound (1) of Example 18.
In a reactor (2 L) 800.5 g of the compound (7) of Example 7 (oleic
sunflower oil ethyl ester--OSOEE) were introduced and 39.4 gl of
formic acid and the whole was left to react at 45.degree. C. for 1
hour at 500 rpm.sup.-1. Hydrogen peroxide was then added dropwise
with a dropping funnel for 36 minutes (355.5 g of H.sub.2O.sub.2
(BAKER)). The whole was then left to react for 2 hours at
75.degree. C. with stirring at 650 rpm.sup.-1. As the reaction is
exothermic, the medium was cooled with a cold water bath.
Washing with water was then carried out until neutrality of the
washing waters. Finally, the residual water was distilled in the
Rotavapor.
1 056.5 g of oleic sunflower epoxidized ethyl esters of the
aforementioned formula (7) were thereby obtained. The product of
formula (7) is in the form of a pale yellow liquid and has a water
content of 0.11%.
Example 19
Preparation of the Diol (8)
This example relates to the preparation of the diol (8) of Example
8 from the compound (7) of Example 1.
In a reactor (2 L) were introduced 100.4 g of compound (7) with 4.1
g (4% by weight) of Amberlyst resin (Aldrich) and 416.1 g of
distilled 1,4-butanediol (Aldrich). The whole was left to react at
70.degree. C. for 4 hours at 650 rpm.sup.-1.
The whole was washed with water for removing the traces of
butanediol, and finally the residual ethanol was distilled in the
Rotavapor.
93.0 g of the polyol of the aforementioned formula (8) were thereby
obtained.
According to the characterization by HPLC chromatography which was
carried out, a composition was obtained, comprising 1.1% by weight
of butanediol, 6.8% by weight of diesters, 70.5% by weight of
monoesters (compound 8) and 2.0% by weight of compound (1).
Example 20
Preparation of Epoxidized Rape Seed Oil Ethyl Esters
This example relates to the preparation of the compound (10) of
Example 10 from erucic rape seed oil ethyl esters.
In a reactor (1 L) are introduced 400.6 g of compound (9) (rape
seed oil ethyl ester--ROEE) and 27.0 g of formic acid and the whole
was left to react at 45.degree. C. for 1 hour at 500 rpm.sup.-1.
Hydrogen peroxide was then added dropwise with a dropping funnel
for 45 minutes (211.1 of H.sub.2O.sub.2 (BAKER)). The whole was
then left to react for 3 hours at 75.degree. C. with stirring at
650 rpm.sup.-1. As the reaction is exothermic, the medium is cooled
with a cold water bath.
Washing with water was then carried out until neutrality of the
washing waters. Finally, the residual water was distilled in the
Rotavapor.
391.1 g of erucic castor oil epoxidized ethyl esters of formula
(10) (cf. Example 10) were thereby obtained.
Example 21
Preparation of the Diol (11)
This example relates to the preparation of the compound (11) of
Example 11 from the ethyl ester of Example 10 of epoxidized erucic
rape seed oil.
In a reactor (2 L) were introduced 350.2 g of compound (10) with
14.3 g (4% by weight) of Amerlyst resin (Aldrich) and 514.5 g of
distilled 1,4-butanediol (Aldrich). The whole was left to react at
70.degree. C. for 4 hours at 650 rpm.sup.-1.
The whole was poured into a separating funnel, in which 200 mL of
warm water were added followed by 100 mL of butanol. After stirring
and phase separation at rest, two phases were observed. The upper
phase was put aside and the lower phase was washed with 2.times.50
mL of butanol. The upper phases were then grouped, washed with warm
water in order to remove the traces of butanediol, and then dried
in the Rotavapor.
272.1 g of a pale yellow liquid with a hydroxyl index of 187.9 mg
KOH/g, as well as a water content of 0.66% were thereby
obtained.
According to the characterization by gas phase chromatography which
was carried out, a composition was obtained comprising less than
0.1% by weight of butanediol, 9.2% by weight of diesters and 66.1%
by weight of monoesters (compound 11).
Example 22
Synthesis of Polyurethanes from the Diols of Examples 19 and 21
Synthesis Procedure
A three-neck flask (250 mL) with a mechanical stirrer and a
nitrogen inlet was loaded with dibutyltin dilaurate (0.003 g, 0.1%
by mass based on the monomers), the polyol (from Example 19 or 21)
(18.0 g, hydroxyl index=215.9) and with isophorone diisocyanate
(IPDI) (6.54 g, OH/NCO=1:0.85). The OH./NCO ratio was calculated on
the basis of the hydroxyl index of the polyol. The reaction medium
was stirred at room temperature under nitrogen flow and heated to
60.degree. C. for 9 hours. Polymerization was controlled by IR
spectroscopy on the basis of the isocyanate band. After completion
of the reaction, 0.7 g of octyl dodecanol were added in order to
stop the reaction with additional heating for a further 12 hours.
The obtained polymer was characterized by IR, MNR and GPC.
The same procedure was applied by using HDMI as a diisocyanate
instead of IPDI.
TABLE-US-00006 TABLE 3 hereafter illustrates the results obtained
for the synthesis of polyurethane by reaction with IPDI or HDMI as
an isocyanate and the polyols of Examples 19 and 21: Viscosity
(cst) 30.degree. C. 80.degree. C. 100.degree. C. OH/NCO GPC
Analysis Shearing (1/s) Polyol ratio diisocyanate Mw Mw/Mn 1 10 1
10 1 10 Ex. 19 1:0.85 IPDI 3280 1.61 5850* -- 105 93 -- 31.5 Ex. 19
1:0.75 HMDI 3210 1.35 6550* -- 98 92 38 33 Ex. 19 1:0.85 HMDI 4160
1.47 -- -- 250 220 95 60 Ex. 21 1:0.7 IPDI 3730 1.32 -- -- -- -- --
--
* * * * *